Lubricating compositions



United StatesPatent O LUBRICATIN G COMPOSITIONS Clarence E. Rannefeld,Pensacola, Fla., assignor to Continental Oil Company, Ponca City, Okla.,a corporation of Delaware No Drawing. Continuation of application SerialNo. 295,338, June 24, 1952. This application June 18, 1954, Serial No.437,883

2 Claims. (Cl. 252-334) This application is a continuation of myco-pending application, Serial No. 295,338, filed June 24, 1952, nowabandoned.

This invention relates to lubricating compositions comprising a base oilof vegetable or mineral origin which may also contain small amounts ofdetergents, corrosion inhibitors, reserve alkalinity agents, and thelike as additives. More particularly, the invention relates to heavyduty crankcase type lubricating oil compositions for use in dieselengines and the like which compositions comprise a major proportion of amineral lubricating oil and minor amounts of an oil soluble detergentand/or an oxidation and corrosion inhibitor and as a reserve alkalinityagent a minor proportion of the barium salt of hydroabietyl alcohol.

Mixtures of dehydroabietyl alcohol, dihydroabietyl alcohol, andtetrahydroabietyl alcohol together with a small proportion of esters ofhydrogenated rosin and hydrocarbons are available commercially under thetrade-mark brand name Abitol by Hercules Powder Company of Wilmington,Delaware. For convenience the material is hereinafter referred to ashydroabietyl alcohol although it is believed to be comprised essentiallyof a mixture of hydrogenated abietyl alcohols containing a non-alcoholfraction amounting to about 13 to 15 percent. The alcohol mixture isthought to be made up of about 15 percent dehydroabietyl alcohol, about40 percent dihydroabietyl. alcohol, and the balance, about 45 percent,tetrahydroabietyl alcohol. The non-alcohol fraction varies wtih thesaponification number but will average about 3 to 8 percent of the totalmixture in the form of esters such as methyl esters of hydrogenatedrosin and the remainder is similar to the hydrocarbon fractionsoccurring in hydrogenated rosin. Although the commercial product is mostreadily available at this time, it is apparent that the use of purerdehydroabietyl alcohol, dihydroabietyl alcohol, and tetrahydroabietylalcohol, either alone or in admixture, in the preparation of alcoholatesfor addition to motor oils, is included within the scope of thisinvention.

The particular improvement of this invention-resides in the addition toa lubricating oil of a barium salt of this hydroabietyl alcohol for thepurpose of increasing the so-called alkaline reserve of the oil. Thefunction of such materials is to neutralize acidity which is formed inthe oil during use or in some manner to counteract the development ofcorrosive conditions formed in the oil during use.

The object of this invention is therefore to provide an improvedlubricating oil composition having a high alkaline reserve content. 7

In preparing the improved oil of this invention, the barium salt ofhydrobietyl alcohol was prepared by mixing a portion of hydroabietylalcohol in S. S. U. pale oil with a substantial excess of barium oxide.The mixture was stirred under a blanket of an inert gas at 205-225 C.for several hours and filtered. The resulting barium alcoholate had ahigh base number and was oil soluble.

Lubricating compositions were then compounded by incorporating a smallamount of barium hydroabietyl alcoholate prepared as above in a mineraloil containing a small proportion of an oil soluble detergent and asulfur-containing corrosion inhibitor. These oil blends were found to behighly basic and, upon test runs in internal combustion engines, werefound to materially decrease the deposits, particularly varnish, uponthe pistons as compared with similar compositions not containing thealcoholate.

Although it is contemplated that the barium hydroabietyl alcoholate maybe incorporated in lubricating oil compositions in amounts ranging fromas little as 0.1 percent to as much as 10 percent, it has been foundthat for most satisfactory results amounts ranging from about 3 to 6percent by weight should be employed. While either calcium diwaxbenzenesulfonate or barium diwaxbenzene sulfonate is shown as the detergent ineach of the following examples, it will be readily apparent that otheroil soluble detergents may also be used. Such detergents may include, byway of example, any of the following: Alkali and alkaline earth metalsalts of (1) petroleum sulfonic acids obtained from the sulfuric acidtreatments of kerosenes, distillate, light oil, wax distillate, or lubeoil stocks, or sulfonic acids from the sulfonation of cracking cyclestocks, gas oil cycle stocks, hydroformer or cycloversion stocks, lubeoil solvent extracts from cresol, phenol, Duosol, furfural,nitrobenzene, or Chlorex extraction of lube oil neutrals, bright stocks,or cylinder stocks, or the above compounds having preferably long chainalkyl su'bstituents as alkylative condensation products of the above;(2) naphthenic acids of mineral origin obtained from kerosene, gasoil,distillate fuel, coal tar, lube oil, and similar stocks by causticextraction, basic solvent extraction, or the like; (3) organiccarboxylic acids such as barium cetyl benzoate, calcium dioctyl acetylsalicylate, strontium alphachloro-phenyl strearate, calciummonochlorstearate, zinc cetyl petrex, calcium octyl petrex, tinamyl-phenyl stearate, and the like; and (4) oil soluble alkyl phenolsand naphthols such as calcium dioxtyl phenolate, sodium nonylnaphtholate, barium diamyl phenolate, potassium diwax-alkylatedphenolate, strontium dinonyl phenolate, and the like. While thedetergent may be present in amounts varying from about 1 to 10 percent,it is preferred to use between about 2 and 5 percent.

Any one of several sulfur-containing corrosion inhibitors may be used asindicated in the examples. In addition.to those specifically mentioned,such other sulfurbearing compounds may be used as: 1) phosphorussulfide-hydrocarbon reaction products such as phosphorus pentasulfidetreated octadecene, phosphorus trisulfide treated cetene, phosphoruspentasulfide treated propylene polymers, phosphorus pentasulfide treatedterpenes, phosphorus pentasulfide treated wax distillate and gas oilolefins, phosphorus pentasulfide treated oil oxidation residues, and thelike; (2) phosphorus sulfide-organic hydroxy reaction products such asphosphorus sulfide treated terpineol, phosphorus sulfidetreated'cyclohex-' phosphorus sulfide treated alkyl substitutednaphthols, phosphorus sulfide treated alkyl substituted phenols,phosphorus sulfide treated cardanol, phosphorus sulfide treated oleylalcohol, and the like; (3) phosphorus sulfide treated fatty acid esterssuch as phosphorus sulfide treated methyl oleate, phosphorus sulfidetreated chlorinated methyl oleate, phosphorus sulfide treated methyllinoleate, phosphorus sulfide treated butyl ricinoleate, phosphorussulfide treated esters of corn oil fatty acid, phosphorus sulfidetreated esters of menhaden oil fatty acid, and the like; (4) sulfur andphosphorus sulfide treated compounds of the above groups particularlycompounds having at least one sulfur or a phosphorus sulfide reactiveolefin grouping or a phosphorus sulfide reactive hydroxy grouping orboth such as sulfur and phosphorus sulfide treated oleic acid, sulfurand phosphorus sulfide treated butyl ricinoleate, sulfur and phosphorussulfide treated 12-hydroxy stearic acid, and the like; sulfurizedcompounds and synthetic sulfides prepared by the action of elementalsulfur on the organic compounds of group (1) about or on the sulfurreactive compounds, particularly mono-olefinic compounds, of groups (2),(3), and (4) above such as sulfur chloride condensed cetyl phenol,sulfur chloride condensed nonyl naphthol, sulfur dichloride condensedwaxylated phenol, sulfur dichloride condensed dioctyl phenol,dioctadecyl sulfide and/or disulfide, and the like.

In addition to the above materials, the alkali metal, alkaline earthmetal, and non-catalytic heavy metal salts of each or any of the abovecomprising the neutralized or partially neutralized phosphorus sulfideor sulfide reaction products may be used. The inhibitor should be addedin amounts such that from'0.l to 0.35 percent sulfur will be present inthe composition.

The preparation of the barium salt of hydroabietyl alcohol will now bedescribed in detail by means of the following example.

4.21 percent barium hydroabietyl alcoholate Balance-mineral lubricatingoil 3 percent calcium diwaxbenzene sulfonate 0.15 percent sulfur asphosphorus pentasulfide treated wax olefin W 4.85 percent bariumhydroabietyl alcoholate Balancemineral lubricating oil Otherformulations were compounded employing other detergents and corrosioninhibitors and in differing proportions as follows:

3 percent calcium diwaxbenzene sulfonate 0.25 percent sulfur as sodiumhydroxide neutralized phos- In each of two 5-liter, 3-necked, flaskswere placed 1,500 grams hydroabietyl alcoholate (Abitol), 1,765 grams of170 pale oil, and 675 grams barium oxide. The barium oxide used was 100percent in excess of the amount theoretically required. These materialswere thoroughly mixed and the mixture was then stirred under a blanketof natural gas at 205225 C. for 6 hours. The material from each batchwas then filtered through diatomaceous earth. The base number of thefirst was 74.5 and of the other 75.7. The two batches were then combinedwith a portion of a third batch prepared in the same manner and thecomposite mixture of 16.67 pounds had a base number of 75.7. Thisresulting barium hydroabietyl alcoholate was then blended with a mineralS. A. E. 30 lubricating oil containing small amounts of calciumdiwaxbenzene sulfonate and sulfur as phosphorus pentasulfide treated waxolefins as shown in the following examples:

3 percent calcium diwaxbenzene sulfonate 0.15 percent sulfur asphosphorus pentasulfide treated wax olefin 3.58 percent bariumhydroabietyl alcoholate Balancemineral lubricating oil 3 percent calciumdiwaxbenzene sulfonate 0.15 percent sulfur as phosphorus pentasulfidetreated wax olefin 3.93 percent barium hydroabietyl alcoholateBalance-mineral lubricating oil III 3 percent calcium diwaxbenzenesulfonate 0.15 percent sulfur as phosphorus pentasulfide treated waxolefin phorus pentasulfide treated wax olefin 4.6 percent bariumhydroabietyl alcoholate Balance-mineral lubricating oil 3 percent bariumdiwaxbenzene sulfonate 0.27 percent sulfur as sulfurized terpene 4.6percent barium hydroabietyl alcoholate Balance-mineral lubricating oilVII 3 percent barium diwaxbenzene sulfonate 0.12 percent sulfur as zincdithiophosphate 4.6 percent barium hydroabietyl alcoholateBalancemineral lubricating oil VIII 3 percent barium diwaxbenzenesulfonate 0.25 percent sulfur as sulfurized wax olefin 4.6 percentbarium hydroabietyl alcoholate Balancemineral lubricating oil Forcomparison purposes the following formulations not containing the bariumhydroabietyl alcoholate were compounded:

2.5 percent calcium diwaxbenzene sulfonate 0.15 percent sulfur asphosphorus pentasulfide treated wax olefin Balance-mineral lubricatingoil 3 percent calcium diwaxbenzene sulfonate 0.15 percent sulfur asphosphorus pentasulfide treated wax olefin Balance-mineral lubricatingoil 6 percent calcium diwaxbenzene sulfonate 3 percent bariumdiwaxbenzene sulfonate 0.15 percent sulfur as phosphorus pentasulfidetreated wax olefin Balance-mineral lubricating oil These severalformulations were then subjected to engine tests, the results of whichare tabulated below.

The compositions of Examples IV, V, VI, VII, VIII, and IX were subjectedto a Cub engine test. This test may be described briefly as follows: Afour-cylinder Cub engine is run for 40 hours at 2,500 R. P. M. with 11brake horsepower output, an oil temperature of 280 F. and a jackettemperature of 200 F. After completion of the run, the parts of theengine are inspected and assigned demerit ratings based on theircondition. The lower the demerit rating, the better is the enginecondition and the oil performance. A rating below 10 is considered to beexcellent and a rating between 10 and 15 is good. The results of thistest are shown in Table I.

Table I Percentage Composition Example No .IV V VI VII VIII IX Calciumdiwaxbenzene sulfonate 3 I 3 2.5 Barium diwaxbenzene sulfonate 3 3 3Sulfur as Pass treated wax olefin 0.15 i 0. Sulfur as NaOHneutralized-Piss treated wax olefin..- 0.25 Sulfur as sulfurized terpeueSulfur as zinc dithiophosphate- Sulfur as sulfurized wax olefin Bariumhydroabietyl alcoholate.-. 4.85 4. 6 4. 4. 6 4.6 None Minerallubricating oil Balance Balance Balance Balance Balance Balance Demerits11 13 13 11 12 17 While the contrasts here are not so striking as thoseTable III obtained in the Witte and Caterpillar tests, it will be seenthat the lubricating oilcompositions show good over-all Percentage comperformance in the engine. Slim The compositions of Examples I, III, IV,and X were subjected to the Witte test which may be described as 5Example II XI follows: Single cylinder Witte engines using a fuel having0 1 1 b a A a cium d wax enzene sulfonate 3 6 an extreme sulfur contentof 2 percent were run for 50 Barium diwaxbenzene 3 hours at 1,800 R. P.M. with about 4 /2-5 brake horse gulfiur as r s m eagea v vax ol ennu0.15 0.15 oa ie y a co 0 a e 3.93 None power output, an oil temperatureof about 145 F. and a lulgricatm on Balance Balance jacket temperatureof 175-180 F. The condltion of the g pistons is examined upon completionof the runs and Demeflts assigned ratings indicating that condition. Ahigh rating is poor and a low rating is good. A Witte piston ratingbelow 4 is considered to be excellent. Those between 4 and about 15 areconsidered to be good to fair and indicate satisfactory performance ofthe lubricating oils while ratings above about 20 indicateunsatisfactory performance. 'The results of this test are shown in TableII.

Table II Percentage Composition Example N o I III IV Calciumdiwaxbenzene sulfonate 3 3 3 3 Sulfur as Pass treated wax ol fin e 0. 150. 15 0.15 0.15 Barium hydroabietyl alcoholate 3. 58 4. 21 4. 85 NoneMineral lubricating oil Balance Balance Balance Balance Witte PistonRating 7 10 8. 5 66-57 The materials used in these test runs differ onlyin barium hydroabietyl alcoholate content. It is seen that the presenceof the alcoholate materially improves the engine performance as comparedwith lubricating oil compositions containing no alcoholate.

Compositions of Examples II and XI were subjected to a l20-hourCaterpillar run with 2 percent sulfur fuel. This test is conducted in asingle cylinder Caterpillar diesel engine at 1,000 R. P. M. withapproximately 20- brake horsepower output, an oil temperature of 145 F.and a jacket temperature of l75-l80 F. At the end of the test run, theparts 'of the engine are inspected and given a demerit rating based onthe condition observed. A demerit rating of zero represents a conditionwherein there are no deposits and a demerit rating of ten represents themaximum deposit that can be formed. Consequently, low demerit ratingsindicate better engine conditions and hence a better performance of theoil in the engine. The results of this test are shown in Table III.

It will accordingly be seen that the rating of the lubricatingcomposition containing barium hydroabietyl alcoholate indicates goodperformance in this test.

The lubricating oil portion of the blends of this invention arepreferably the so-called mineral or hydrocarbon oils but may alsoconsist of wholly or contain in part certain fatty oils including cornoil, soybean oil, lard oil, and the like. The blends may likewisecontain voltolized oils or synthetic oils of lubricating viscosity.Mineral oil is meant to include oils refined from any of the variouscrude oils refined by any of the usual refining processes includingdistillation, solvent extraction, acid treatment, clay treatment,dewaxing, and the like.

It will be understood that in addition to the ingredients in the aboverecited formations, small amounts of other materials, all of which areconventional in this field, may be added as necessary and desired. Theseinclude antifoaming agents, pour-point depressants, material to im provethe oiliness of the composition, and the like.

It is apparent that many modifications and variations of the inventionas hereinbefore set forth may be made without departing from the spiritand scope thereof. The examples given are by way of illustration onlyand the invention is limited only by the terms of the appended claims.

I claim:

1. A lubricating composition comprising from about 2 to 5% of an oilsoluble calcium diwaxbenzene sulfonate, at least 0.15 percent sulfur asphosphorus penta sulfide treated wax olefin, from about 3 to 6% of aproduct obtained by reacting a hydroabietyl alcohol wherein said alcoholcomprises a mixture of hydrogenated abietyl alcohols containing anon-alcohol fraction amounting to about 13 to 15 percent and the alcoholfraction comprising about 15 percent dehydroabietyl alcohol, about 40percent dihydroabietyl alcohol and about 45 percent tetrahydroabietylalcohol with an amount of barium oxide in excess of that which willreact stoichiometrically with said alcohol in a lubricating oil under aninert atmosphere and at a temperature of 205 to 225 C., and the balancea mineral lubricating oil.

2. A lubricating composition comprising from about 2 to 5% of an oilsoluble calcium diwaxbenzene sulfonate, from about 0.10 to 0.35% sulfuras sulfurized wax olefin, from about 3 to 6% of a product obtainedbyreacting a hydroabietyl alcohol wherein said alcohol comprises I amixture of hydrogenated abietyl alcohols containing a I non-alcoholfraction amounting to about 13' to 15 percent and the alcohol fractioncomprising about '15 percent dehydroabietyl alcohol, about 40 percentdihydroabietyl al' cohol and about 45 percent tetrahyd'r'oabietylalcohol with an amount of barium oxide in excess of that which willreact stoichiometrically with said alcohol in a lubricating oil under aninert atmosphere and at a temperature of 205 to 225 C., and the balancea mineral lubricating oil.

References Cited in the file of this patent UNITED STATES PATENTS

1. A LUBRICATING COMPOSITION COMPRISING FROM ABOUT 2 TO 5% OF AN OILSOLUBLE CALCIUM DIWAXBENZENE SULFONATE, AT LEAST 0.15 PERCENT SULFUR ASPHOSPHORUS PENTA SULFIDE TREATED WAX OLEFIN, FROM ABOUT 3 TO 6% OF APRODUCT OBTAINED BY REACTING A HYDROABIETYL ALCOHOL WHEREIN SAID ALCOHOLCOMPRISES A MIXTURE OF HYDROGENATED ABIETYL ALCOHOLS CONTAINING ANON-ALCOHOL FRACTION AMOUNTING TO ABOUT 13 TO 15 PERCENT AND THE ALCOHOLFRACTION COMPRISING ABOUT 15 PERCENT HYDROABIETYL ALCOHOL, ABOUT 40PERCENT DIHYDROABIETYL ALCOHOL AND ABOUT 45 PERCENT TETRAHYDROABIETYLALCOHOL WITH AN AMOUNT OF BARIUM OXIDE IN EXCESS OF THAT WHICH WILLREACT STOICHIOMETRICALLY WITH SAID ALCOHOL IN A LUBRICATING OIL UNDER ANINERT ATMOSPHERE AND AT A TEMPERATURE OF 205 TO 225* C., AND THE BALANCEA MINERAL LUBRICATING OIL.